Janda A.Vlaisavljevich B.Lin L.-C.Mallikarjun Sharada S.Smit B.Head-Gordon M.Bell A.T.LI-CHIANG LIN2022-05-242022-05-242015https://www.scopus.com/inward/record.uri?eid=2-s2.0-84929352983&doi=10.1021%2facs.jpcc.5b01715&partnerID=40&md5=9ae8419cc5b943aa0c728ced9f815dbehttps://scholars.lib.ntu.edu.tw/handle/123456789/611508Experimental measurements of the rate coefficient (kapp) and apparent enthalpies and entropies of activation (ΔHapp and ΔSapp) for alkane cracking catalyzed by acidic zeolites can be used to characterize the effects of zeolite structure and alkane size on the intrinsic enthalpy and entropy of activation, (Formula presented.) and (Formula presented.). To determine (Formula presented.) and (Formula presented.), enthalpies and entropies of adsorption, ΔHads-H+ and ΔSads-H+, must be determined for alkane molecules moving from the gas phase to Br?nsted acid sites at reaction temperatures (>673 K). Experimental values of ΔHapp and ΔSapp must also be properly defined in terms of ΔHads-H+ and ΔSads-H+. We report here a method for determining ΔHads-H+ and ΔSads-H+ in which the adsorption site is represented by a fixed volume that includes the proton. Values of ΔHads-H+ and ΔSads-H+ obtained from Monte Carlo simulations are in good agreement with values obtained from experimental data measured at 300-400 K. An important feature of the simulations, however, is their ability to account for the redistribution of alkane adsorbed at protons in different locations with increasing temperature. Values of (Formula presented.) and (Formula presented.) for the cracking of propane through n-hexane, determined from measured values of kapp and ΔHapp and simulated values of ΔHads-H+ and ΔSads-H+, agree well with values obtained independently from quantum mechanics/molecular mechanics calculations. Application of our method of analysis reveals that the observed increase in kapp with increasing n-alkane size is due primarily to a decrease in (Formula presented.) with increasing chain length and that (Formula presented.) is independent of chain length. ? 2015 American Chemical Society.AdsorptionChain lengthChainsChemical activationCracksEnthalpyEntropyHexaneIntelligent systemsMolecular modelingMonte Carlo methodsQuantum theoryThermodynamicsZeolitesActivation parameterAdsorption thermodynamicsEntropy of activationExperimental valuesImportant featuresIncreasing temperaturesQuantum mechanics/molecular mechanicsReaction temperatureParaffinsjournal article10.1021/acs.jpcc.5b017152-s2.0-84929352983